Chapter 6 Covalent bonding. Makes molecules Specific atoms joined by sharing electrons Molecular...

Chapter 6

Covalent bonding

Covalent bonding

Makes molecules Specific atoms joined by sharing electrons

Molecular compound Sharing by different elements

Diatomic molecules Two of the same atom O2 N2

Diatomic elements

There are 8 elements that always form molecules

H2 , N2 , O2 , F2 , Cl2 , Br2 , I2 , and At2

Oxygen by itself means O2

The –ogens and the –ines 1 + 7 pattern on the periodic table

1 and 7

Molecular compounds

Tend to have low melting and boiling points Have a molecular formula which shows

type and number of atoms in a molecule Not necessarily the lowest ratio (empirical

formula C6H12O6

No ions…non conductors (electrolytes)

How does H2 form?

The nuclei repel

++

How does H2 form?

++

The nuclei repel But they are attracted to electrons They share the electrons

Covalent bonds

Nonmetals hold onto their valence electrons.

They can’t give away electrons to bond. Still need noble gas configuration. Get it by sharing valence electrons with

each other. By sharing both atoms get to count the

electrons toward noble gas configuration.

Covalent bonding Fluorine has seven valence electrons A second atom also has seven By sharing electrons Both end with full orbitals

F F

Covalent bonding Fluorine has seven valence electrons A second atom also has seven By sharing electrons Both end with full orbitals

F F8 Valence electrons

Covalent bonding Fluorine has seven valence electrons A second atom also has seven By sharing electrons Both end with full orbitals

F F8 Valence electrons

Single Covalent Bond

A sharing of two valence electrons. Only nonmetals and Hydrogen. Different from an ionic bond because they

actually form molecules. Two specific atoms are joined. In an ionic solid you can’t tell which atom

the electrons moved from or to.

How to show how they formed

It’s like a jigsaw puzzle. I have to tell you what the final formula is. You put the pieces together to end up with

the right formula. For example- show how water is formed

with covalent bonds.

Water

H

O

Each hydrogen has 1 valence electron

and wants 1 more

The oxygen has 6 valence electrons

and wants 2 more

They share to make each other “happy”

Water

Put the pieces together The first hydrogen is happy The oxygen still wants one more

H O

Water

The second hydrogen attaches Every atom has full energy levels

H OH

Multiple Bonds

Sometimes atoms share more than one pair of valence electrons.

A double bond is when atoms share two pair (4) of electrons.

A triple bond is when atoms share three pair (6) of electrons.

Carbon dioxide

CO2 - Carbon is central atom

Carbon has 4 valence electrons

Wants 4 more Oxygen has 6 valence

electrons Wants 2 more

O

C

Carbon dioxide

Attaching 1 oxygen leaves the oxygen 1 short and the carbon 3 short

OC

Carbon dioxide Attaching the second oxygen leaves

both oxygen 1 short and the carbon 2 short

OCO

Carbon dioxide The only solution is to share more

OCO

Carbon dioxide The only solution is to share more

OCO

Carbon dioxide The only solution is to share more

OCO

Carbon dioxide The only solution is to share more

OCO

Carbon dioxide The only solution is to share more

OCO

Carbon dioxide The only solution is to share more

OCO

Carbon dioxide The only solution is to share more Requires two double bonds Each atom gets to count all the atoms in

the bond

OCO

Carbon dioxide The only solution is to share more Requires two double bonds Each atom gets to count all the atoms in

the bond

OCO8 valence electrons

Carbon dioxide The only solution is to share more Requires two double bonds Each atom gets to count all the atoms in

the bond

OCO8 valence electrons

Carbon dioxide The only solution is to share more Requires two double bonds Each atom gets to count all the atoms in

the bond

OCO

8 valence electrons

How to draw them To figure out if you need multiple bonds Add up all the valence electrons. Count up the total number of electrons to

make all atoms happy. Subtract. Divide by 2 Tells you how many bonds - draw them. Fill in the rest of the valence electrons to fill

atoms up.

Examples

NH3 N - has 5 valence electrons wants 8 H - has 1 valence electrons wants 2 NH3 has 5+3(1) = 8 NH3 wants 8+3(2) = 14 (14-8)/2= 3 bonds 4 atoms with 3 bonds

N

H

N HHH

Examples

Draw in the bonds All 8 electrons are accounted for Everything is full

Examples

HCN C is central atom N - has 5 valence electrons wants 8 C - has 4 valence electrons wants 8 H - has 1 valence electrons wants 2 HCN has 5+4+1 = 10 HCN wants 8+8+2 = 18 (18-10)/2= 4 bonds 3 atoms with 4 bonds -will require multiple bonds -

not to H

HCN

Put in single bonds Need 2 more bonds Must go between C and N

NH C

HCN

Put in single bonds Need 2 more bonds Must go between C and N Uses 8 electrons - 2 more to add

NH C

HCN

Put in single bonds Need 2 more bonds Must go between C and N

NH C

Where do bonds go?

Think of how many electrons they are away from noble gas.

H should form 1 bond- always O should form 2 bonds – if possible N should form 3 bonds – if possible C should form 4 bonds– if possible

Practice

Draw electron dot diagrams for the following.

PCl3

H2O2

CH2O

C3H6

Another way of indicating bonds

Often use a line to indicate a bond Called a structural formula Each line is 2 valence electrons

H HO =H HO

Structural Examples

H C N

C OH

H

C has 8 electrons because each line is 2 electrons

Coordinate Covalent Bond

When one atom donates both electrons in a covalent bond.

Carbon monoxide CO

OC

Coordinate Covalent Bond

When one atom donates both electrons in a covalent bond.

Carbon monoxide

OC

Coordinate Covalent Bond

When one atom donates both electrons in a covalent bond.

OCOC

How do we know if

Have to draw the diagram and see what happens.

Often happens with polyatomic ions If an element has the wrong number of

bonds

Polyatomic ions

Groups of atoms held by covalent bonds, with a charge

Can’t build directly, use (happy-have)/2 Have number will be different Surround with [ ], and write charge NH4

2+

ClO21-

Resonance

When more than one dot diagram with the same connections is possible.

Choice for double bond

NO2-

Which one is it? Does it go back and forth? Double bonds are shorter than single In NO2

- all the bonds are the same length

Resonance

It is a mixture of both, like a mule.

CO32-

Bond Dissociation Energy

The energy required to break a bond C - H + 393 kJ C + H Double bonds have larger bond dissociation

energies than single Triple even larger

C-C 347 kJ C=C 657 kJ C≡C 908 kJ

Bond Dissociation Energy

The larger the bond energy, the harder it is to break

Large bond energies make chemicals less reactive.

VSEPR Valence Shell Electron Pair Repulsion. Predicts three dimensional geometry of

molecules. Name tells you the theory. Valence shell - outside electrons. Electron Pair repulsion - electron pairs try to

get as far away as possible. Can determine the angles of bonds. And the shape of molecules

VSEPR

Based on the number of pairs of valence electrons both bonded and unbonded.

Unbonded pair are called lone pair. CH4 - draw the structural formula

VSEPR

Single bonds fill all atoms.

There are 4 pairs of electrons pushing away.

The furthest they can get away is 109.5º.

C HH

H

H

4 atoms bonded

Basic shape is tetrahedral.

A pyramid with a triangular base.

Same basic shape for everything with 4 pairs.

CH HH

H109.5º

3 bonded - 1 lone pair

N HH

H

NH HH

<109.5º

Still basic tetrahedral but you can’t see the electron pair.

Shape is calledtrigonal pyramidal.

2 bonded - 2 lone pair

OH

H

O HH

<109.5º

Still basic tetrahedral but you can’t see the 2 lone pair.

Shape is calledbent.

3 atoms no lone pair

CH

HO

The farthest you can the electron pair apart is 120º.

Shape is flat and called trigonal planar.

C

H

H O

120º

2 atoms no lone pair

With three atoms the farthest they can get apart is 180º.

Shape called linear. Will require 2 double bonds or one triple bond

C OO180º

Molecular Orbitals

The overlap of atomic orbitals from separate atoms makes molecular orbitals

Each molecular orbital has room for two electrons

Two types of MO Sigma ( σ ) between atoms Pi ( π ) above and below atoms

Sigma bonding orbitals

From s orbitals on separate atoms

+ +

s orbital s orbital

+ ++ +

Sigma bondingmolecular orbital

Sigma bonding orbitals

From p orbitals on separate atoms

p orbital p orbital

Sigma bondingmolecular orbital

Pi bonding orbitals

P orbitals on separate

atoms

Pi bondingmolecular orbital

Sigma and pi bonds

All single bonds are sigma bonds A double bond is one sigma and one pi

bond A triple bond is one sigma and two pi

bonds.

Hybrid Orbitals

Combines bonding with geometry

Hybridization

The mixing of several atomic orbitals to form the same number of hybrid orbitals.

All the hybrid orbitals that form are the same. sp3 -1 s and 3 p orbitals mix to form 4 sp3 orbitals. sp2 -1 s and 2 p orbitals mix to form 3 sp2 orbitals

leaving 1 p orbital. sp -1 s and 1 p orbitals mix to form 2 sp orbitals

leaving 2 p orbitals.

Hybridization

109.5º with s and p Need 4 orbitals. We combine one s orbital and 3 p orbitals. Make sp3 hybrid sp3 hybridization has tetrahedral geometry.

sp3 geometry

109.5º

This leads to tetrahedral shape.

Every molecule with a total of 4 atoms and lone pair is sp3 hybridized.

Gives us trigonal pyramidal and bent shapes also.

How we get to hybridization

We know the geometry from experiment. We know the orbitals of the atom hybridizing atomic orbitals can explain the

geometry. So if the geometry requires a 109.5º bond

angle, it is sp3 hybridized.

sp2 hybridization

C2H4

double bond counts as one pair

Two trigonal planar sections Have to end up with three blended orbitals use one s and two p orbitals to make sp2

orbitals. leaves one p orbital perpendicular

C C

H

HH

H

Where is the P orbital?

Perpendicular The overlap of

orbitals makes a sigma bond ( bond)

Two types of Bonds

Sigma bonds ( from overlap of orbitals between the atoms Pi bond ( bond) between p orbitals. above and below atoms All single bonds are

bonds Double bond is 1

and 1 bond Triple bond is 1

and 2 bonds

CCH

H

H

H

sp2 hybridization

when three things come off atom trigonal planar 120º one bond

What about two

when two things come off one s and one p hybridize linear

sp hybridization

end up with two lobes 180º apart.

p orbitals are at right angles makes room for two bonds

and two sigma bonds. a triple bond or two double

bonds

CO2 C can make two and two O can make one and one

CCOO OO

N2

N2

Polar Bonds

When the atoms in a bond are the same, the electrons are shared equally.

This is a nonpolar covalent bond. When two different atoms are connected,

the electrons may not be shared equally. This is a polar covalent bond. How do we measure how strong the atoms

pull on electrons?

Electronegativity

A measure of how strongly the atoms attract electrons in a bond.

The bigger the electronegativity difference the more polar the bond.

Use table 12-3 Pg. 285 0.0 - 0.3 Covalent nonpolar 0.4 - 1.7 Covalent moderately polar >1.7 Ionic

How to show a bond is polar Isn’t a whole charge just a partial charge means a partially positive means a partially negative

The Cl pulls harder on the electrons The electrons spend more time near the Cl

H Cl

Polar Molecules

Molecules with ends

Polar Molecules Molecules with a partially positive end and

a partially negative end Requires two things to be true The molecule must contain polar bonds This can be determined from

differences in electronegativity.Symmetry can not cancel out the effects of

the polar bonds.Must determine geometry first.

Polar Molecules Symmetrical shapes are those without lone

pair on central atom Tetrahedral Trigonal planar Linear

Will be nonpolar if all the atoms are the same

Shapes with lone pair on central atom are not symmetrical

Can be polar even with the same atom

Is it polar?

HF H2O

NH3

CCl4

CO2

CH3Cl

H - F+ -

H - F

+-H - F+

-

H - F

+-

H - F +-

H - F+-

H - F

+-

H - F

+-

+-

Intermolecular Forces

What holds molecules to each other

Intermolecular Forces

They are what make solid and liquid molecular compounds possible.

The weakest are called van der Waal’s forces - there are two kinds Dispersion forces Dipole Interactions

Dispersion Force

Depends only on the number of electrons in the molecule

Bigger molecules more electrons More electrons stronger forces

F2 is a gasBr2 is a liquidI2 is a solid

Dipole interactions

Occur when polar molecules are attracted to each other.

Slightly stronger than dispersion forces. Opposites attract but not completely hooked

like in ionic solids.

Dipole interactions

Occur when polar molecules are attracted to each other.

Slightly stronger than dispersion forces. Opposites attract but not completely hooked

like in ionic solids.

H F

H F

Dispersion force

H H H HH H H H

+ -

H H H H

+ - +

Hydrogen bonding

Are the attractive force caused by hydrogen bonded to F, O, or N.

F, O, and N are very electronegative so it is a very strong dipole.

They are small, so molecules can get close together

The hydrogen partially share with the lone pair in the molecule next to it.

The strongest of the intermolecular forces.

Hydrogen Bonding

HH

O+ -

+

H HO+-

+

Hydrogen bonding

HH

O H HO

HH

O

H

H

OH

HO

H

HO HH

O

Properties of Molecular Compounds Made of nonmetals Poor or nonconducting as solid, liquid or

aqueous solution Low melting point Two kinds of crystals

Molecular solids held together by IMF Network solids- held together by bonds One big molecule (diamond, graphite)